CN114230059A - Method for removing 2-chlorophenol in water by using thermally activated persulfate - Google Patents
Method for removing 2-chlorophenol in water by using thermally activated persulfate Download PDFInfo
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- CN114230059A CN114230059A CN202111315864.9A CN202111315864A CN114230059A CN 114230059 A CN114230059 A CN 114230059A CN 202111315864 A CN202111315864 A CN 202111315864A CN 114230059 A CN114230059 A CN 114230059A
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- persulfate
- chlorophenol
- wastewater
- water
- aqueous solution
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- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 title claims abstract description 105
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical class S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000002351 wastewater Substances 0.000 claims abstract description 118
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 239000002738 chelating agent Substances 0.000 claims abstract description 28
- 238000012986 modification Methods 0.000 claims abstract description 22
- 230000004048 modification Effects 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- 239000011268 mixed slurry Substances 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 33
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 33
- 239000010865 sewage Substances 0.000 claims description 28
- 230000015556 catabolic process Effects 0.000 claims description 22
- 238000006731 degradation reaction Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 239000008394 flocculating agent Substances 0.000 claims description 7
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 7
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 230000005684 electric field Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000889 atomisation Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 230000016615 flocculation Effects 0.000 abstract 1
- 238000005189 flocculation Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 description 31
- 239000003054 catalyst Substances 0.000 description 21
- 238000002156 mixing Methods 0.000 description 18
- 230000001105 regulatory effect Effects 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- -1 persulfate ions Chemical class 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000004659 sterilization and disinfection Methods 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 229920001661 Chitosan Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 1
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention discloses a method for removing 2-chlorophenol in water by using thermally activated persulfate, which comprises the following steps: s1, carrying out flocculation precipitation treatment on the wastewater containing 2-chlorophenol, and then adjusting the pH and the salt content; s2, preparing a sulfate aqueous solution, adding a chelating agent into the persulfate aqueous solution, and performing ultrasonic dispersion treatment to obtain a pre-modified solution; completely immersing the powdered activated carbon into water to obtain mixed slurry, and then adding a pre-modification liquid into the mixed slurry to react to obtain modified persulfate; s3, adding the modified persulfate into the wastewater treated in the step S1, and then introducing high-pressure water vapor into the wastewater to obtain primary purified wastewater; adsorbing and purifying the primary purified wastewater by using an activated carbon adsorption column to obtain purified wastewater; the invention has reasonable design and utilizes heat to activate S2O8 2‑Can effectively degrade the 2-chlorophenol in the wastewater and improve the safety of wastewater discharge.
Description
Technical Field
The invention relates to the technical field of organic wastewater treatment, in particular to a method for removing 2-chlorophenol in water by utilizing thermally activated persulfate.
Background
Dichlorophenol is a toxic and non-degradable pollutant and is widely present in production wastewater of pesticides, dyes, plasticizers and the like. Countries such as the united states and china have blacklisted harmful substances or preferred pollutants in water. Therefore, how to eliminate the pollution of chlorophenol compounds in the environment is a subject of great importance. Currently, with the increasing requirements on environmental protection and sustainable development, the methods for removing chlorophenols are roughly classified into: three physical methods, biological methods and chemical methods. Physical methods generally use adsorbents such as activated carbon, chitosan, bentonite, etc. for adsorption. The activated carbon is a very good adsorbent, is simple to prepare and wide in raw material, and researchers have made activated carbon from straw, waste rubber, coal, coconut shell and wood to adsorb chlorophenol pollutants, so that a very good effect is achieved. The chitosan molecule contains free amino and hydroxyl, and the amino can be protonated to form cations, so that the chitosan has strong adsorption capacity to anions and amphoteric compounds. Bentonite is also used for the adsorption research of chlorophenol organic matters, a biological method is to degrade pollutants by screening and domesticating microorganisms, biodegradation is a commonly used treatment method in sewage treatment, and researchers at home and abroad at present have some researches on the biodegradation of chlorophenol pollutants and obtain certain achievements. The chemical method generally adopts a reduction or oxidation mode to achieve the purpose of degrading the chlorophenol compounds. The reduction method includes zero-valent iron (Fe) reduction, ultrasonic/zero-valent iron system reduction and the like. Examples of the oxidation method include fenton reagent oxidation, supercritical wet oxidation, and electrochemical oxidation.
Strong oxidation techniques based on activated persulfates are relatively mature and widely used worldwide, but the following disadvantages remain in the application process: 1. the temperature of the wastewater has great influence on the decomposition rate of persulfate, and the purification effect of the wastewater is influenced; 2. the pH value needs to be stabilized in the optimal alkaline range to be most beneficial to oxidation during alkali activation, but the pH value falls back to neutral after general wastewater purification needs to be repaired, so that water body alkalization is avoided, and the requirement on the adding amount of alkali during practical operation is higher; 3. the alkaline pH may fall back as the reaction continues, requiring timely replenishment of alkali to maintain optimal reaction conditions, or otherwise reducing oxidation efficiency.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for efficiently and economically removing 2-chlorophenol in water by using thermally activated persulfate.
The technical scheme of the invention is as follows: a method for removing 2-chlorophenol in water by using thermally activated persulfate comprises the following steps:
s1, adjusting water quality;
s1-1, introducing the waste water containing 2-chlorophenol into a pretreatment tank, adding a flocculating agent into the pretreatment tank according to the addition amount of 1-3 wt%, then stirring at the rotating speed of 1250-2500 r/min for 30-55 min, finally filtering the waste water containing 2-chlorophenol, and introducing into an adjusting tank;
s1-2, adding H with the mass concentration of 1.0mol/L into a regulating reservoir2SO4Adjusting the pH value of the filtered wastewater to 3-10 by using a solution or a NaOH solution; finally, adjusting the salt content in the wastewater to 1-3 wt%;
s2, thermally modifying with persulfate;
s2-1, preparing a persulfate aqueous solution with the mass concentration of 3-5 mmol/L, then adding a chelating agent into the persulfate aqueous solution, and performing dispersion treatment for 20-45 min at the ultrasonic frequency of 300-590 kHz; obtaining a pre-modification liquid; wherein; the adding amount of the chelating agent is 0.2-0.5 mg/L, and the chelating agent is a mixture consisting of copper sulfate, calcium oxide and ferric chloride according to the mass ratio of 1:2: 1;
s2-2, completely immersing powdered activated carbon with the particle size of 0.5-0.8 mm in water, fully stirring to obtain mixed slurry, adding the pre-modified liquid obtained in the step S2-1, wherein the volume of the powdered activated carbon is 45-65% of that of the mixed slurry, controlling the temperature of a reaction system to be 45-95 ℃, stirring for reaction for 30-60 min, separating the powdered activated carbon after the reaction is finished, and drying at 63-78 ℃ to obtain modified persulfate;
s3, 2-chlorophenol catalytic degradation;
s3-1, adding the modified persulfate obtained in the step S2-2 into an adjusting tank according to the adding proportion of 8-22 mg/L, pumping high-pressure steam into the adjusting tank through a pipeline, wherein the pressure of the high-pressure steam is 1.2-2.5 MPa, the temperature is 50-70 ℃, and reacting at constant temperature for 40-80 min to obtain primary purified wastewater;
s3-2, carrying out adsorption purification on the primary purified wastewater obtained in the step S3-1 by using an activated carbon adsorption column with the particle size of 150-320 meshes to obtain purified wastewater.
Further, in step S1-1, after the wastewater containing 2-chlorophenol is introduced into the pretreatment tank, H is added into the pretreatment tank2O2And stirring uniformly; wherein H2O2The volume ratio of the sewage to the sewage is 1: 16-24, and H is added into a pretreatment tank2O2The method can carry out preoxidation decomposition on the waste water containing 2-chlorophenol, and obviously reduce the content of 2-chlorophenol in the waste water.
Further, before the step S2-1, uniformly mixing persulfate, iron phosphide and deionized water according to the mass ratio of 1:3:8, and then carrying out ultrasonic dispersion for 20-45 min at the frequency of 120-160 kHz; and (3) obtaining a mixed solution, mixing persulfate, iron phosphide and deionized water, performing ultrasonic dispersion treatment, and activating persulfate to generate persulfate free radicals by utilizing the synergistic action of zero-valent iron and ultrasonic waves so as to degrade 2-chlorophenol in the wastewater to achieve the effect of wastewater treatment.
Further, in the step S3-1, preparing the modified persulfate into an aqueous solution with the mass concentration of 4-7 mmol/L, spraying the aqueous solution into an adjusting tank in a turntable atomization manner, and exciting the atomized aqueous solution by using a high-frequency high-voltage electric field with the voltage of 15-25 kV and the frequency of 10-20 kHz to generate plasma; the plasma carries a large amount of persulfate free radicals, hydroxyl free radicals and high-energy electrons, the oxidation capacity is extremely high, and the jet-type jet stirrer is used for enabling the sewage to be in full contact reaction with the persulfate free radicals, the hydroxyl free radicals and the high-energy electrons, so that the degradation of the 2-chlorophenol in the sewage is promoted.
Further, after the step S2-1 is finished, adding zero-valent iron into the pre-modification liquid, wherein the zero-valent iron is 10-25 wt% of the volume of the pre-modification liquid; the zero-valent iron is derived from nano zero-valent iron or iron waste of a processing plant; promoting the zero-valent iron to activate the free radicals generated by the persulfate to directly oxidize the 2-chlorophenol, thereby providing the degradation rate of the 2-chlorophenol in the sewage and improving the activation rate of the persulfate.
Further, in step S2-1, the persulfate is one of potassium persulfate, sodium persulfate, and ammonium persulfate; s produced during thermal activation of persulfate2O8 2-The free radicals can effectively degrade the 2-chlorophenol in the wastewater.
Further, in step S1-1, the flocculating agent is one of sodium polyacrylate and polyaluminium chloride; the flocculant is utilized to enable suspended particles in the wastewater to lose stability, colloid phases are mutually condensed to form flocculating constituents, and finally precipitates are formed under the action of gravity to be filtered, so that the difficulty of the post-treatment of the wastewater is reduced.
Further, after completion of step S3-2, ClO is first utilized2Sterilizing the purified wastewater, and detecting the purified wastewater by adopting a high performance liquid chromatography-tandem mass spectrometry; through carrying out disinfection treatment and detection to purifying waste water, can improve the security of purifying sewage discharge.
Further, after the step S3-1 is finished, introducing the primary purified wastewater into a photo reactor for reaction, irradiating for 5-15 min by using ultraviolet light with the power of 15-28W, and continuously stirring the primary purified wastewater in the irradiation process; by using the UV advanced oxidation process, persulfate ions are promoted to be generated by oxidative decomposition of persulfate, the rate of degrading 2-chlorophenol by persulfate is increased, and the treatment efficiency of 2-chlorophenol sewage is increased.
Further, after the step S2-1 is completed, adding a catalyst with the volume of 8-15 wt% into the pre-modification solution, and fully and uniformly mixing, wherein the preparation method of the catalyst comprises the following steps: 1) mixing ammonium chlorideUniformly mixing the mixture with a tetraethyl silicate solution in the same volume, and reacting for 15-45 hours at the temperature of 90-110 ℃ to obtain a mixture A; 2) mixing the mixture A with FeCl3·6H2Uniformly mixing O according to the volume ratio of 1: 3-4 to obtain a mixture B; 3) filtering the mixture B, calcining the precipitate at 350-650 ℃ for 0.5-1.6 h, and naturally cooling to obtain the required catalyst; by adding the catalyst prepared by the invention, persulfate in the pre-modified liquid can be effectively activated, so that strong oxidizing radicals are generated by decomposition, and 2-chlorophenol in a polluted water body is mineralized and degraded; meanwhile, compared with the traditional catalyst, the catalyst provided by the invention has the advantages of excellent performance, low cost and stable performance.
Compared with the prior art, the invention has the beneficial effects that: the invention has reasonable design, can effectively promote the degradation of 2-chlorophenol in the wastewater and improve the safety of wastewater discharge; by carrying out thermal activation treatment on persulfate, the contact time of persulfate free radicals and organic pollutants such as 2-chlorophenol is prolonged by utilizing the high oxidation-reduction potential and the relatively long half-life period of the persulfate free radicals, so that the degradation of the 2-chlorophenol is facilitated; meanwhile, compared with hydroxyl radicals, the persulfate radicals have better activity under neutral and alkaline conditions, the applicable pH range is wide, and some pollutants that the hydroxyl radicals cannot oxidize, namely the persulfate radicals, can also be degraded, so that the method has higher practicability and popularization and application values; meanwhile, the method has guiding significance for treating organic wastes such as chlorophenol by removing 2-chlorophenol in water by using thermally activated persulfate.
Detailed Description
Example 1: a method for removing 2-chlorophenol in water by using thermally activated persulfate comprises the following steps:
s1, adjusting water quality;
s1-1, introducing the waste water containing 2-chlorophenol into a pretreatment tank, adding a flocculating agent into the pretreatment tank according to the addition amount of 1 wt%, then stirring at 1250r/min for 30min, finally filtering the waste water containing 2-chlorophenol, and introducing into an adjusting tank;
s1-2, adding H with the mass concentration of 1.0mol/L into the adjusting tank2SO4Adjusting the pH value of the filtered wastewater to 3; finally, adjusting the salt content in the wastewater to 1 wt%;
s2, thermally modifying with persulfate;
s2-1, preparing a persulfate aqueous solution with the mass concentration of 3mmol/L, then adding a chelating agent into the persulfate aqueous solution, and performing dispersion treatment for 20min at the ultrasonic frequency of 300 kHz; obtaining a pre-modification liquid; wherein; the adding amount of the chelating agent is 0.2mg/L, and the chelating agent is a mixture consisting of copper sulfate, calcium oxide and ferric chloride according to the mass ratio of 1:2: 1;
s2-2, completely immersing powdered activated carbon with the particle size of 0.5-0.7 mm in water, fully stirring to obtain mixed slurry, adding the pre-modified liquid obtained in the step S2-1, wherein the volume of the powdered activated carbon is 45%, into the mixed slurry, controlling the temperature of a reaction system to be 45 ℃, stirring and reacting for 30min, separating the powdered activated carbon after the reaction is finished, and drying at 63 ℃ to obtain modified persulfate;
s3, 2-chlorophenol catalytic degradation;
s3-1, adding the modified persulfate obtained in the step S2-2 into an adjusting tank according to the adding proportion of 8mg/L, pumping high-pressure steam into the adjusting tank through a pipeline, wherein the pressure of the high-pressure steam is 1.2MPa, the temperature of the high-pressure steam is 50 ℃, and reacting at constant temperature for 40min to obtain primary purified wastewater;
s3-2, carrying out adsorption purification on the primary purified wastewater obtained in the step S3-1 by using an activated carbon adsorption column with the granularity of 150 meshes to obtain purified wastewater.
Example 2: a method for removing 2-chlorophenol in water by using thermally activated persulfate comprises the following steps:
s1, adjusting water quality;
s1-1, introducing the wastewater containing 2-chlorophenol into a pretreatment tank, and firstly adding H into the pretreatment tank2O2And stirring uniformly; wherein H2O2The volume ratio of the sewage to the sewage is 1:16, and H is added into a pretreatment tank2O2Can be used for the application of 2-Carrying out preoxidation decomposition on chlorophenol wastewater to remarkably reduce the content of 2-chlorophenol in the wastewater, then adding a sodium polyacrylate flocculant into a pretreatment tank according to the addition amount of 2 wt%, then carrying out stirring treatment for 45min at the rotating speed of 1850r/min, and finally carrying out filtration treatment on the wastewater containing 2-chlorophenol and introducing the wastewater into an adjusting tank;
s1-2, adding H with the mass concentration of 1.0mol/L into a regulating reservoir2SO4Adjusting the pH value of the filtered wastewater to 5; finally, adjusting the salt content in the wastewater to be 2 wt%;
s2, thermally modifying with persulfate;
s2-1, preparing a potassium persulfate aqueous solution with the mass concentration of 4mmol/L, then adding a chelating agent into the potassium persulfate aqueous solution, and performing dispersion treatment for 33min at the ultrasonic frequency of 450 kHz; obtaining a pre-modification liquid; wherein; the adding amount of the chelating agent is 0.3mg/L, and the chelating agent is a mixture consisting of copper sulfate, calcium oxide and ferric chloride according to the mass ratio of 1:2: 1;
s2-2, completely immersing powdered activated carbon with the particle size of 0.6-0.8 mm in water, fully stirring to obtain mixed slurry, adding the pre-modified liquid obtained in the step S2-1, wherein the volume of the powdered activated carbon is 52%, into the mixed slurry, controlling the temperature of a reaction system to be 78 ℃, stirring and reacting for 45min, separating the powdered activated carbon after the reaction is finished, and drying at the temperature of 70 ℃ to obtain modified potassium persulfate;
s3, 2-chlorophenol catalytic degradation;
s3-1, adding the modified potassium persulfate obtained in the step S2-2 into an adjusting tank according to the adding proportion of 13mg/L, pumping high-pressure steam into the adjusting tank through a pipeline, wherein the pressure of the high-pressure steam is 1.8MPa, the temperature is 65 ℃, and reacting at constant temperature for 50min to obtain primary purified wastewater;
s3-2, carrying out adsorption purification on the primary purified wastewater obtained in the step S3-1 by using an activated carbon adsorption column with the granularity of 255 meshes to obtain purified wastewater.
Example 3: a method for removing 2-chlorophenol in water by using thermally activated persulfate comprises the following steps:
s1, adjusting water quality;
s1-1, introducing the waste water containing 2-chlorophenol into a pretreatment tank, adding a polyaluminium chloride flocculant into the pretreatment tank according to the addition amount of 3 wt%, stirring at the rotating speed of 2500r/min for 55min, finally filtering the waste water containing 2-chlorophenol, and introducing into an adjusting tank;
s1-2, adding a NaOH solution with the mass concentration of 1.0mol/L into the regulating reservoir, and regulating the pH value of the filtered wastewater to 6; finally, adjusting the salt content in the wastewater to 3 wt%;
s2, thermally modifying with persulfate;
s2-1, uniformly mixing potassium persulfate, iron phosphide and deionized water according to the mass ratio of 1:3:8, and then carrying out ultrasonic dispersion for 20min at the frequency of 120kHz to obtain a mixed solution; potassium persulfate, iron phosphide and deionized water are mixed and then subjected to ultrasonic dispersion treatment, and the synergistic effect of zero-valent iron and ultrasonic waves is utilized to activate potassium persulfate to generate persulfate radicals, so that 2-chlorophenol in wastewater is degraded, and the effect of wastewater treatment is achieved; then preparing the mixed solution into a potassium persulfate aqueous solution with the mass concentration of 5mmol/L, adding a chelating agent into the potassium persulfate aqueous solution, and performing dispersion treatment for 45min at the ultrasonic frequency of 590 kHz; obtaining a pre-modification liquid; wherein; the adding amount of the chelating agent is 0.5mg/L, and the chelating agent is a mixture consisting of copper sulfate, calcium oxide and ferric chloride according to the mass ratio of 1:2: 1; adding zero-valent iron into the pre-modification liquid, wherein the zero-valent iron accounts for 10 wt% of the volume of the pre-modification liquid; the zero-valent iron is derived from nano zero-valent iron or iron waste of a processing plant; promoting the zero-valent iron to activate the free radicals generated by the persulfate to directly oxidize the 2-chlorophenol, thereby providing the degradation rate of the 2-chlorophenol in the sewage and improving the activation rate of the persulfate;
s2-2, completely immersing powdered activated carbon with the particle size of 0.6-0.8 mm in water, fully stirring to obtain mixed slurry, adding the pre-modified liquid obtained in the step S2-1, wherein the volume of the powdered activated carbon is 65%, into the mixed slurry, controlling the temperature of a reaction system to be 95 ℃, stirring and reacting for 60min, separating the powdered activated carbon after the reaction is finished, and drying at the temperature of 78 ℃ to obtain modified potassium persulfate;
s3, 2-chlorophenol catalytic degradation;
s3-1, adding the modified potassium persulfate obtained in the step S2-2 into an adjusting tank according to the adding proportion of 22mg/L, pumping high-pressure steam into the adjusting tank through a pipeline, wherein the pressure of the high-pressure steam is 2.5MPa, the temperature is 70 ℃, and after constant-temperature reaction for 60min, obtaining primary purified wastewater;
s3-2, carrying out adsorption purification on the primary purified wastewater obtained in the step S3-1 by using an activated carbon adsorption column with the granularity of 320 meshes to obtain purified wastewater.
Example 4: a method for removing 2-chlorophenol in water by using thermally activated persulfate comprises the following steps:
s1, adjusting water quality;
s1-1, introducing the waste water containing 2-chlorophenol into a pretreatment tank, adding a sodium polyacrylate flocculant into the pretreatment tank according to the addition amount of 1 wt%, then stirring at the rotating speed of 1250r/min for 30min, finally filtering the waste water containing 2-chlorophenol, and introducing into an adjusting tank;
s1-2, adding a NaOH solution with the mass concentration of 1.0mol/L into the regulating reservoir, and regulating the pH value of the filtered wastewater to 8; finally, adjusting the salt content in the wastewater to be 2 wt%;
s2, thermally modifying with persulfate;
s2-1, preparing a potassium persulfate aqueous solution with the mass concentration of 3mmol/L, then adding a chelating agent into the potassium persulfate aqueous solution, and performing dispersion treatment for 20min at the ultrasonic frequency of 300 kHz; obtaining a pre-modification liquid; wherein; the adding amount of the chelating agent is 0.2mg/L, and the chelating agent is a mixture consisting of copper sulfate, calcium oxide and ferric chloride according to the mass ratio of 1:2: 1;
s2-2, completely immersing powdered activated carbon with the particle size of 0.5-0.6 mm in water, fully stirring to obtain mixed slurry, adding the pre-modified liquid obtained in the step S2-1, wherein the volume of the powdered activated carbon is 45%, into the mixed slurry, controlling the temperature of a reaction system to be 45 ℃, stirring and reacting for 30min, separating the powdered activated carbon after the reaction is finished, and drying at 63 ℃ to obtain modified potassium persulfate;
s3, 2-chlorophenol catalytic degradation;
s3-1, preparing the modified potassium persulfate into an aqueous solution with the mass concentration of 4mmol/L, spraying the aqueous solution into an adjusting tank in a turntable atomization mode according to the adding proportion of 8mg/L, and exciting the atomized aqueous solution by utilizing a high-frequency high-voltage electric field of 15kV and 10kHz to generate plasma; the plasma carries a large amount of persulfate free radicals, hydroxyl free radicals and high-energy electrons, the oxidation capacity is extremely high, and the jet-type jet stirrer is used for enabling the sewage to be in full contact reaction with the persulfate free radicals, the hydroxyl free radicals and the high-energy electrons so as to promote the degradation of the 2-chlorophenol in the sewage; then pumping high-pressure steam into the regulating reservoir through a pipeline, wherein the pressure of the high-pressure steam is 1.22MPa, the temperature is 50 ℃, and reacting for 80min at constant temperature to obtain primary purified wastewater; introducing the primary purified wastewater into a photoreactor for reaction, irradiating for 5min by using ultraviolet light with the power of 15W, and continuously stirring the primary purified wastewater in the irradiation process; by using the UV advanced oxidation process, potassium persulfate is promoted to be oxidized and decomposed to generate persulfate ions, the rate of degrading 2-chlorophenol by potassium persulfate is increased, and the treatment efficiency of 2-chlorophenol sewage is increased;
s3-2, carrying out adsorption purification on the primary purified wastewater obtained in the step S3-1 by using an activated carbon adsorption column with the granularity of 150 meshes to obtain purified wastewater.
Example 5: a method for removing 2-chlorophenol in water by using thermally activated persulfate comprises the following steps:
s1, adjusting water quality;
s1-1, introducing the waste water containing 2-chlorophenol into a pretreatment tank, adding a sodium polyacrylate flocculant into the pretreatment tank according to the addition amount of 3 wt%, then stirring at the rotating speed of 2500r/min for 55min, finally filtering the waste water containing 2-chlorophenol, and introducing into an adjusting tank;
s1-2, adding a NaOH solution with the mass concentration of 1.0mol/L into the regulating reservoir, and regulating the pH value of the filtered wastewater to 10; finally, adjusting the salt content in the wastewater to 3 wt%;
s2, thermally modifying with persulfate;
s2-1, preparing a potassium persulfate aqueous solution with the mass concentration of 5mmol/L, then adding a chelating agent into the potassium persulfate aqueous solution, and performing dispersion treatment for 45min at the ultrasonic frequency of 590 kHz; obtaining a pre-modification liquid; wherein; the adding amount of the chelating agent is 0.5mg/L, and the chelating agent is a mixture consisting of copper sulfate, calcium oxide and ferric chloride according to the mass ratio of 1:2: 1;
s2-2, completely immersing powdered activated carbon with the particle size of 0.5-0.6 mm in water, fully stirring to obtain mixed slurry, adding the pre-modified liquid obtained in the step S2-1, wherein the volume of the powdered activated carbon is 65%, into the mixed slurry, controlling the temperature of a reaction system to be 95 ℃, stirring and reacting for 60min, separating the powdered activated carbon after the reaction is finished, and drying at the temperature of 78 ℃ to obtain modified potassium persulfate;
s3, 2-chlorophenol catalytic degradation;
s3-1, adding the modified potassium persulfate obtained in the step S2-2 into an adjusting tank according to the adding proportion of 22mg/L, pumping high-pressure steam into the adjusting tank through a pipeline, wherein the pressure of the high-pressure steam is 2.52MPa, the temperature is 70 ℃, and carrying out constant-temperature reaction for 40min to obtain primary purified wastewater;
s3-2, carrying out adsorption purification on the primary purified wastewater obtained in the step S3-1 by using an activated carbon adsorption column with the granularity of 320 meshes to obtain purified wastewater; post-lease utilization of ClO2Sterilizing the purified wastewater; after the disinfection treatment, detecting the purified wastewater by adopting a high performance liquid chromatography-tandem mass spectrometry method; through carrying out disinfection treatment and detection to purifying waste water, can improve the security of purifying sewage discharge.
Example 6: a method for removing 2-chlorophenol in water by using thermally activated persulfate comprises the following steps:
s1, adjusting water quality;
s1-1, introducing the waste water containing 2-chlorophenol into a pretreatment tank, adding a sodium polyacrylate flocculant into the pretreatment tank according to the addition amount of 3 wt%, then stirring at the rotating speed of 2500r/min for 55min, finally filtering the waste water containing 2-chlorophenol, and introducing into an adjusting tank;
s1-2, adding a NaOH solution with the mass concentration of 1.0mol/L into the regulating reservoir, and regulating the pH value of the filtered wastewater to 10; finally, adjusting the salt content in the wastewater to 3 wt%;
s2, thermally modifying with persulfate;
s2-1, preparing a sodium persulfate aqueous solution with the mass concentration of 5mmol/L, then adding a chelating agent into the sodium persulfate aqueous solution, and performing dispersion treatment for 45min at the ultrasonic frequency of 590 kHz; obtaining a pre-modification liquid; wherein; the adding amount of the chelating agent is 0.4mg/L, and the chelating agent is a mixture consisting of copper sulfate, calcium oxide and ferric chloride according to the mass ratio of 1:2: 1; adding a catalyst with the volume of 8 wt% into the pre-modification liquid, and fully and uniformly mixing, wherein the preparation method of the catalyst comprises the following steps: 1) uniformly mixing ammonium chloride and tetraethyl silicate solution in equal volume, and reacting at 90 ℃ for 15h to obtain a mixture A; 2) mixing the mixture A with FeCl3·6H2Mixing O uniformly according to the volume ratio of 1:3 to obtain a mixture B; 3) filtering the mixture B, calcining the precipitate at 350 ℃ for 0.5h, and naturally cooling to obtain the required catalyst; by adding the catalyst prepared by the invention, persulfate in the pre-modified liquid can be effectively activated, so that strong oxidizing radicals are generated by decomposition, and 2-chlorophenol in a polluted water body is mineralized and degraded; meanwhile, compared with the traditional catalyst, the catalyst provided by the invention has the advantages of excellent performance, low cost and stable performance;
s2-2, completely immersing powdered activated carbon with the particle size of 0.5-0.7 mm in water, fully stirring to obtain mixed slurry, adding the pre-modified liquid obtained in the step S2-1, wherein the volume of the powdered activated carbon is 45%, into the mixed slurry, controlling the temperature of a reaction system to be 45 ℃, stirring and reacting for 30min, separating the powdered activated carbon after the reaction is finished, and drying at 63 ℃ to obtain modified sodium persulfate;
s3, 2-chlorophenol catalytic degradation;
s3-1, adding the modified sodium persulfate obtained in the step S2-2 into an adjusting tank according to the adding proportion of 22mg/L, pumping high-pressure steam into the adjusting tank through a pipeline, wherein the pressure of the high-pressure steam is 2.5MPa, the temperature is 70 ℃, and carrying out constant-temperature reaction for 40min to obtain primary purified wastewater;
s3-2, carrying out adsorption purification on the primary purified wastewater obtained in the step S3-1 by using an activated carbon adsorption column with the granularity of 320 meshes to obtain purified wastewater.
Example 7: a method for removing 2-chlorophenol in water by using thermally activated persulfate comprises the following steps:
s1, adjusting water quality;
s1-1, introducing the wastewater containing 2-chlorophenol into a pretreatment tank, and firstly adding H into the pretreatment tank2O2And stirring uniformly; wherein H2O2The volume ratio of the sewage to the sewage is 1:24, and H is added into a pretreatment tank2O2The method can be used for carrying out preoxidation decomposition on the waste water containing 2-chlorophenol, remarkably reducing the content of 2-chlorophenol in the waste water, then adding a polyaluminium chloride flocculating agent into a pretreatment tank according to the adding amount of 3 wt%, then carrying out stirring treatment for 55min at the rotating speed of 2500r/min, finally carrying out filtration treatment on the waste water containing 2-chlorophenol, and introducing the waste water into an adjusting tank;
s1-2, adding a NaOH solution with the mass concentration of 1.0mol/L into the regulating reservoir, and regulating the pH value of the filtered wastewater to 10; finally, adjusting the salt content in the wastewater to 3 wt%;
s2, thermally modifying with persulfate;
s2-1, uniformly mixing potassium persulfate, iron phosphide and deionized water according to the mass ratio of 1:3:8, and then carrying out ultrasonic dispersion for 45min at the frequency of 160kHz to obtain a mixed solution; mixing potassium persulfate, iron phosphide and deionized water, performing ultrasonic dispersion treatment, activating persulfate to generate persulfate free radicals by utilizing the synergistic action of zero-valent iron and ultrasonic waves so as to degrade 2-chlorophenol in wastewater to achieve the effect of wastewater treatment, preparing the mixed solution into a potassium persulfate aqueous solution with the mass concentration of 5mmol/L, adding a chelating agent into the potassium persulfate aqueous solution, and performing dispersion treatment for 45min at the ultrasonic frequency of 590 kHz; obtaining a pre-modification liquid; wherein; the adding amount of the chelating agent is 0.5mg/L, and the chelating agent is a mixture consisting of copper sulfate, calcium oxide and ferric chloride according to the mass ratio of 1:2: 1; adding zero-valent iron into the pre-modification liquid, wherein the zero-valent iron accounts for 25 wt% of the volume of the pre-modification liquid; the zero-valent iron is derived from nano zero-valent iron or iron waste of a processing plant; promoting the zero-valent iron to activate the free radical generated by the potassium persulfate to directly oxidize the 2-chlorophenol, thereby providing the degradation rate of the 2-chlorophenol in the sewage and improving the activity of the potassium persulfateA rate of change; finally, adding a catalyst with the volume of 15 wt% into the pre-modification liquid, and fully and uniformly mixing, wherein the preparation method of the catalyst comprises the following steps: 1) uniformly mixing ammonium chloride and tetraethyl silicate solution in equal volume, and reacting for 45 hours at the temperature of 110 ℃ to obtain a mixture A; 2) mixing the mixture A with FeCl3·6H2Mixing O uniformly according to the volume ratio of 1:4 to obtain a mixture B; 3) filtering the mixture B, calcining the precipitate at 650 ℃ for 1.6h, and naturally cooling to obtain the required catalyst; by adding the catalyst prepared by the invention, potassium persulfate in the pre-modified liquid can be effectively activated, so that strong oxidizing radicals are generated by decomposition, and 2-chlorophenol in a polluted water body is mineralized and degraded; meanwhile, compared with the traditional catalyst, the catalyst provided by the invention has the advantages of excellent performance, low cost and stable performance;
s2-2, completely immersing powdered activated carbon with the particle size of 0.6-0.8 mm in water, fully stirring to obtain mixed slurry, adding the pre-modified liquid obtained in the step S2-1, wherein the volume of the powdered activated carbon is 65%, into the mixed slurry, controlling the temperature of a reaction system to be 95 ℃, stirring to react for 30min, separating the powdered activated carbon after the reaction is finished, and drying at the temperature of 78 ℃ to obtain modified potassium persulfate;
s3, 2-chlorophenol catalytic degradation;
s3-1, preparing the modified potassium persulfate into an aqueous solution with the mass concentration of 7mmol/L, spraying the aqueous solution into an adjusting tank in a turntable atomization mode according to the adding proportion of 22mg/L, and exciting the atomized aqueous solution by utilizing a high-frequency high-voltage electric field of 25kV and 20kHz to generate plasma; carrying a large amount of persulfate free radicals, hydroxyl free radicals and high-energy electrons in the plasma, wherein the persulfate free radicals, the hydroxyl free radicals and the high-energy electrons have extremely strong oxidizing capability, the sewage is fully contacted and reacted with the persulfate free radicals, the hydroxyl free radicals and the high-energy electrons through a jet flow type jet stirrer to promote the degradation of 2-chlorophenol in the sewage, and finally high-pressure steam is pumped into an adjusting tank through a pipeline, the pressure of the high-pressure steam is 2.5MPa, the temperature is 70 ℃, and the constant-temperature reaction is carried out for 40min to obtain primary purified wastewater; introducing the primary purified wastewater into a photoreactor for reaction, irradiating for 15min by using ultraviolet light with the power of 28W, and continuously stirring the primary purified wastewater in the irradiation process; by using the UV advanced oxidation process, potassium persulfate is promoted to be oxidized and decomposed to generate persulfate ions, the rate of degrading 2-chlorophenol by potassium persulfate is increased, and the treatment efficiency of 2-chlorophenol sewage is increased;
s3-2, carrying out adsorption purification on the primary purified wastewater obtained in the step S3-1 by using an activated carbon adsorption column with the granularity of 320 meshes to obtain purified wastewater; finally utilizing ClO2Sterilizing the purified wastewater; after the disinfection treatment, detecting the purified wastewater by adopting a high performance liquid chromatography-tandem mass spectrometry method; through carrying out disinfection treatment and detection to purifying waste water, can improve the security of purifying sewage discharge.
Test example:
firstly, respectively and equivalently collecting 24 parts of 2-chlorophenol-polluted water in a certain chemical plant in south China, and randomly dividing 24 parts of 2-chlorophenol-polluted water samples into 8 groups with equivalent quantities; wherein, the first 7 groups of polluted water samples are respectively treated by the methods of the embodiments 1 to 7 of the invention, and the 8 th group of polluted water samples are treated by the method of the prior art to be used as comparative examples;
secondly, after the treatment is finished, separating each group of polluted water body samples through a C18 reverse phase chromatographic column (Hitachi LaChrom,5 mu m multiplied by 250mm multiplied by 4.6mm), wherein the mobile phase comprises methanol (60%) and water (40%), the flow rate is 1 mL/min < -1 >, and the sample injection amount is 40 mu L; the detector adopts a Diode Array (DAD), and the quantitative wavelength is 274 nm; calculating the average degradation rate of the 2-chlorophenol in each group of polluted water samples; the calculation results are shown in table 1:
table 1 effect of the method of each example on the degradation rate of 2-chlorophenol in a contaminated water body;
thirdly, analyzing results;
as can be seen from the data in Table 1, compared with the prior art, the method disclosed by the invention can effectively promote the degradation of 2-chlorophenol in the polluted water body; example 2 in comparison to example 1, by adding H to the pretreatment tank2O2The pre-oxidation decomposition can be carried out on the waste water containing 2-chlorophenol, so that the content of 2-chlorophenol in the waste water is obviously reduced; compared with the embodiment 1, the embodiment 3 has the advantages that persulfate, iron phosphide and deionized water are mixed and subjected to ultrasonic dispersion treatment, and the persulfate is activated by utilizing the synergistic action of zero-valent iron and ultrasonic waves to generate persulfate radicals so as to degrade 2-chlorophenol in wastewater, so that the wastewater treatment effect is achieved; zero-valent iron is added into the pre-modification liquid, so that the 2-chlorophenol can be directly oxidized by radicals generated by activating persulfate by the zero-valent iron, the degradation rate of the 2-chlorophenol in sewage is increased, and the activation rate of the persulfate is increased; compared with the embodiment 1, the embodiment 4 has the advantages that the atomized water solution is excited by the high-frequency high-voltage electric field to generate plasma, the plasma carries a large amount of persulfate free radicals, hydroxyl free radicals and high-energy electrons, the oxidation capacity is extremely strong, the sewage is enabled to be in full contact reaction with the persulfate free radicals, the hydroxyl free radicals and the high-energy electrons through the jet-type jet stirrer, and the degradation of 2-chlorophenol in the sewage is promoted; by using the UV advanced oxidation process, persulfate ions are promoted to be generated by oxidative decomposition of persulfate, the rate of degrading 2-chlorophenol by persulfate is increased, and the treatment efficiency of 2-chlorophenol sewage is increased; example 5 compared with example 1, the safety of the purified wastewater discharge can be improved by performing the disinfection treatment and the detection on the purified wastewater; compared with the embodiment 1, the embodiment 6 has the advantages that the catalyst prepared by the method can be added to effectively activate persulfate in the pre-modified liquid, so that strong oxidizing radicals are generated by decomposition, and the 2-chlorophenol in the polluted water body is mineralized and degraded; meanwhile, compared with the traditional catalyst, the catalyst provided by the invention has the advantages of excellent performance, low cost and stable performance; compared with 1-6, the embodiment 7 integrates and optimizes all favorable conditions, so that the removal rate of the 2-chlorophenol in the wastewater is highest.
Claims (10)
1. A method for removing 2-chlorophenol in water by using thermally activated persulfate is characterized by comprising the following steps:
s1, adjusting water quality;
s1-1, introducing the waste water containing 2-chlorophenol into a pretreatment tank, adding a flocculating agent into the pretreatment tank according to the addition amount of 1-3 wt%, stirring at the rotating speed of 1250-2500 r/min for 30-55 min, filtering the waste water containing 2-chlorophenol, and introducing into an adjusting tank;
s1-2, adding H with the mass concentration of 1.0mol/L into the adjusting tank2SO4Adjusting the pH value of the filtered wastewater to 3-10 by using a solution or a NaOH solution; finally, adjusting the salt content in the wastewater to 1-3 wt%;
s2, thermally modifying with persulfate;
s2-1, preparing a persulfate aqueous solution with the mass concentration of 3-5 mmol/L, then adding a chelating agent into the persulfate aqueous solution, and performing dispersion treatment for 20-45 min at the ultrasonic frequency of 300-590 kHz; obtaining a pre-modification liquid; wherein; the adding amount of the chelating agent is 0.2-0.5 mg/L, and the chelating agent is a mixture consisting of copper sulfate, calcium oxide and ferric chloride according to the mass ratio of 1:2: 1;
s2-2, completely immersing powdered activated carbon with the particle size of 0.5-0.8 mm in water, fully stirring to obtain mixed slurry, adding the pre-modified liquid obtained in the step S2-1, wherein the volume of the powdered activated carbon is 45-65% of that of the mixed slurry, controlling the temperature of a reaction system to be 45-95 ℃, stirring for reaction for 30-60 min, separating the powdered activated carbon after the reaction is finished, and drying at 63-78 ℃ to obtain modified persulfate;
s3, 2-chlorophenol catalytic degradation;
s3-1, adding the modified persulfate obtained in the step S2-2 into an adjusting tank according to the adding proportion of 8-22 mg/L, pumping high-pressure steam into the adjusting tank, wherein the pressure of the high-pressure steam is 1.2-2.5 MPa, the temperature is 50-70 ℃, and reacting at constant temperature for 40-80 min to obtain primary purified wastewater;
s3-2, carrying out adsorption purification on the primary purified wastewater obtained in the step S3-1 by using an activated carbon adsorption column with the particle size of 150-320 meshes to obtain purified wastewater.
2. The method for removing 2-chlorophenol in water by using heat-activated persulfate as claimed in claim 1, wherein, in step S1-1, after the wastewater containing 2-chlorophenol is introduced into the pretreatment tank, H is added into the pretreatment tank2O2And stirring uniformly; wherein, the H2O2The volume ratio of the sewage to the sewage is 1: 16-24.
3. The method for removing 2-chlorophenol in water by using heat-activated persulfate according to claim 1, wherein before the step S2-1, persulfate, iron phosphide and deionized water are uniformly mixed according to a mass ratio of 1:3:8, and then ultrasonic dispersion is carried out at a frequency of 120-160 kHz for 20-45 min.
4. The method for removing 2-chlorophenol in water by using heat-activated persulfate according to claim 1, wherein in step S3-1, the modified persulfate is prepared into an aqueous solution with a mass concentration of 4-7 mmol/L, and then the aqueous solution is sprayed into an adjusting tank in a turntable atomization manner, and then a high-frequency high-voltage electric field of 15-20 KV and 10-15 kHz is used for exciting the atomized aqueous solution to generate plasma.
5. The method for removing 2-chlorophenol in water by using thermally activated persulfate according to claim 1, wherein after step S2-1 is completed, zero-valent iron is added into the pre-modification solution, and the zero-valent iron accounts for 10-25 wt% of the volume of the pre-modification solution; the zero-valent iron is derived from nano zero-valent iron or iron waste of a processing plant.
6. The method for removing 2-chlorophenol according to claim 1, wherein in step S2-1, the persulfate is one of potassium persulfate, sodium persulfate, and ammonium persulfate.
7. The method for removing 2-chlorophenol according to claim 1, wherein in step S1-1, the flocculating agent is one of sodium polyacrylate and polyaluminium chloride.
8. The method for removing 2-chlorophenol in water by using heat-activated persulfate according to claim 1, wherein after completion of step S3-2, ClO is first used2And (3) sterilizing the purified wastewater, and then detecting the purified wastewater by adopting a high performance liquid chromatography-tandem mass spectrometry.
9. The method for removing 2-chlorophenol in water by using thermally activated persulfate according to claim 1, wherein after the step S3-1 is completed, the primary purified wastewater is introduced into a photoreactor for reaction, and is irradiated by ultraviolet light with the power of 15-28W for 5-15 min, and the primary purified wastewater is continuously stirred in the process of illumination.
10. The method for removing 2-chlorophenol according to claim 1, wherein in step S1-1, the flocculating agent is sodium polyacrylate and polyaluminium chloride.
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